JP2009279829A - Glass-containing heat transfer sheet - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide the structure of a glass-containing heat transfer sheet which is prepared by an extrusion molding method using a glass-containing molding composition and has a glass-containing protective layer containing glass with a glass compounding rate of 40 to 70 wt.%, and to provide characteristics and properties of the glass-containing heat transfer sheet. <P>SOLUTION: The glass-containing heat transfer sheet is made by laminating a releasing layer, the protective layer and an adhesive layer on a sheet-like substrate, wherein the protective layer contains globular glass powder of a glass compounding rate of 40 to 70 wt.% and a functional filler in a thermoplastic resin, the surface of the protective layer includes flattened parts made of the thermoplastic resin and global convex parts formed by a large number of globular glass powders covered with the thermoplastic resin, and a part of the functional filler is protruded from the flattened parts and globular convex parts. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a glass-containing thermal transfer sheet having a protective layer containing spherical glass powder used for molded products used for home appliances, furniture and the like, decorative plywood and the like. More specifically, the present invention relates to a glass-containing thermal transfer sheet having a protective layer in which the spherical glass powder is contained in a thermoplastic resin at a glass blending ratio of 40 to 70% by weight.

The production results of plastic products such as films / sheets, containers, machinery / equipment / parts, and plates in Japan are about 58.83 million tons in 2002 and about 6.39 million tons in 2006. It shows an increase of .6% and continues to increase by an average of 1.9% every year.
Among the plastic moldings mentioned above, the containers in particular were about 640,000 tons (11% of total production) in 2002 and about 820,000 tons (13% of total production) in 2006. In the meantime, it shows an increase of 28.1%, and on average it continues to increase by 5.6% every year.

By the way, Japan's plastic production volume in 2004 reached about 1.48 million tons, and the production volume of thermoplastic resin occupies the top among plastics, and about 90% of the production volume of plastic is thermoplastic resin. The production volume is expected to increase in the future.
The inventor of the present invention devised day by day in order to solve the global warming problem such as carbon dioxide and the finite oil resource depletion problem which are urgently solved as a global problem today. As a result, if a molding composition can be molded by mixing a large amount of glass powder into a thermoplastic resin, for example, 70% by weight of glass powder, kneading and extruding with an extruder. For example, the inventors have thought that the amount of thermoplastic resin used can be reduced by 70%, and the amount of carbon dioxide emission can be reduced by 70%.

  Therefore, the inventor has filed a patent application as Japanese Patent Application No. 2008-129263 for the invention of the invention “Glass-containing molding composition and method for producing the same” before filing the present application. By removing the cause of the sudden drop in fluidity caused by the increase in the glass powder content in the resin, molding is possible even when glass powder with a glass content of 40 to 70% by weight is blended in the thermoplastic resin. The present invention provides a molding composition, a method for producing the molding composition, the characteristics of the molding composition, and a global warming problem such as carbon dioxide, which is urgently required to be solved as a global problem. The purpose of the present invention is to provide a solution to the finite oil resource depletion problem. According to the invention, spherical glass powder is contained in a thermoplastic resin at a glass content of 40 to 70% by weight. Molding of the molding composition is has become possible.

  In the conventional molding technique, a molding composition containing a spherical glass powder in a glass blending ratio of 40% by weight or more in a thermoplastic resin could not be molded. Therefore, the glass-containing molding composition was used. A protective layer (hereinafter referred to as “glass-containing protective layer”) containing a spherical glass powder in a thermoplastic resin used for the glass-containing thermal transfer sheet produced by an extrusion molding method is naturally not known.

  Therefore, the inventor molded the glass-containing molding composition, and the glass-containing protective layer contained in the glass blending ratio of 40 to 70% by weight using the molding composition by an extrusion molding method. A glass-containing thermal transfer sheet is prepared by laminating a release layer on a sheet-like substrate, a glass-containing protective layer thereon, and an adhesive layer, and the properties and physical properties of the glass-containing thermal transfer sheet are obtained. As a result of investigation, it was found that there are new characteristics and physical properties that are not found in conventional heat-sensitive sheets, and the present invention has been completed.

  Therefore, the present invention provides a glass-containing thermal transfer sheet having a glass-containing protective layer that is produced by an extrusion molding method using the glass-containing molding composition and is contained at a glass blending ratio of 40 to 70% by weight. The purpose is to provide the structure and its properties and properties.

In order to achieve the above object, the glass-containing thermal transfer sheet of the invention according to claim 1 is a glass-containing thermal transfer sheet in which a release layer, a protective layer and an adhesive layer are provided in a laminated form on a sheet-like substrate. The protective layer contains spherical glass powder having a glass blending ratio of 40 to 70% by weight and a functional filler in the thermoplastic resin, and the surface of the protective layer is a flat portion made of the thermoplastic resin, It consists of a spherical convex part formed with many spherical glass powders coat | covered with the thermoplastic resin, and a part of said functional filler protrudes from this flat part and a spherical convex part, It is characterized by the above-mentioned.
The glass-containing thermal transfer sheet of the invention according to claim 2 is characterized in that the sheet-like substrate is a film containing a spherical glass powder having a glass blending ratio of 40 to 70% by weight in a thermoplastic resin.
The glass-containing thermal transfer sheet of the invention according to claim 3 is characterized in that the sheet-like substrate is selected from paper or one of cellophane, PET, PA, and PI films.
The glass-containing thermal transfer sheet of the invention according to claim 4 is characterized in that the functional filler is one type or two or more types selected from an antibacterial agent, a flame retardant, an antistatic agent, an electromagnetic shielding agent, and a conductive agent. And
The glass-containing thermal transfer sheet of the invention according to claim 5 is characterized in that the functional filler has a particle size smaller than that of the spherical glass powder.
The glass-containing thermal transfer sheet of the invention according to claim 6 is characterized in that printing or metal vapor deposition is applied to the glass-containing protective layer.
The glass-containing thermal transfer sheet of the invention according to claim 7 is characterized in that the spherical glass powder has an average particle size of 2 to 40 μm.

The glass-containing thermal transfer sheet having the glass-containing protective layer of the present invention is a glass-containing molding composition that has been impossible to mold by blending 40% by weight or more of glass powder in a thermoplastic resin in the prior art. The product can be molded by containing glass powder having a glass blending ratio of 40 to 70% by weight, and the glass-containing thermal transfer sheet produced by an extrusion molding method using the composition can also be obtained. It was.
As a result, when the glass-containing thermal transfer sheet is incinerated, the amount of carbon dioxide emitted can be reduced by up to 70%, which solves the global warming problem caused by carbon dioxide, which is a global issue. Great contribution as technology.
In addition, the present invention can greatly reduce the amount of thermoplastic resin, that is, the amount of petroleum used by 70%, and has a great contribution as a technology for dealing with the finite oil resource depletion problem that is a global issue.

And this invention makes resin contain the glass powder of the maximum 70% remaining after the incineration of the said molded object, and shape | molds the glass-containing molding composition again, A 70% glass powder is repeated many times. It can be recycled and contributes greatly as a technology that forms a recycling-oriented society.
Furthermore, since the raw material for spherical glass powder is an abundant resource in Japan and its material cost is low, it is promising as an alternative material for today's rapidly increasing oil.

The glass-containing thermal transfer sheet of the present invention is transferred to the surface of final products such as home appliances, furniture, molded articles, decorative plywood, etc., and the glass-containing protective layer on the transferred surface has a surface hardness of 2H. Since it is hard as described above, it is possible to protect the final product, for example, a rubber sheet laid on the floor, from being damaged.
And, since a part of the functional filler protrudes from the spherical convex portion formed in the glass-containing protective layer of the transferred surface, antibacterial action provided with the functional filler, antistatic action, electromagnetic wave shielding action, And a conductive effect can be exhibited effectively.

First, the glass-containing molding composition of Japanese Patent Application No. 2008-129263 (hereinafter referred to as “the glass-containing molding composition and its manufacturing method”) (hereinafter referred to as the “prior application invention”) filed prior to the filing of the present application. The contents will be described, and then the “glass-containing thermal transfer sheet” of the present invention will be described.
Explaining the contents of the glass-containing molding composition is that the protective layer and the sheet-like substrate of the glass-containing thermal transfer sheet are produced by an extrusion molding method using the glass-containing molding composition, By explaining how to mold a glass-containing molding composition, it is understood that a glass-containing molding composition can be molded from a glass powder having a glass content of 40 to 70% by weight and a thermoplastic resin material. This is to make it easier.

(The glass-containing molding composition)
FIG. 1 is a longitudinal sectional view of a single-screw extruder that is an example of an extruder used in a manufacturing method for forming a glass-containing molding composition of the prior invention and producing the composition. The glass-containing molding composition is molded by kneading and extruding a spherical glass powder having a glass blending ratio of 40 to 70% by weight and a thermoplastic resin by the extruder.

A process of forming a glass-containing molding composition by kneading and extruding 40 to 70% by weight of spherical glass powder and a thermoplastic resin will be described with reference to the single-screw extruder of FIG.
The main structure of the single screw extruder used in the embodiment of the invention of the prior application is composed of a hopper, a motor, a speed reducer, a screw, a cylinder, a heater / blower (heating / cooling device), etc., and an adapter is attached to the tip of the cylinder. A nozzle die is attached via In the case of conventional kneading and extruding processes using only a thermoplastic resin, a thermoplastic resin molding material (hereinafter referred to as “pellet”) fed into the hopper is sent to the right along the screw thread. However, the heater temperature is set according to the type of resin.

  The single-screw extruder is provided with two hoppers for charging pellets and spherical glass powder as feed materials. The hoppers of the extruder shown in FIG. 1 are referred to as first and second hoppers in order from the left side. The first hopper is filled with thermoplastic resin pellets, and the second hopper provided near the middle part of the extruder Is charged with spherical glass powder. The arrangement position of the second hopper is provided at a position where the pellets supplied from the first hopper into the screw barrel are in a molten state along with the kneading and conveying by the screw.

  The extruder provided with the first and second hoppers has been conventionally known as a resin material and a plurality of types of fillers, pigments, etc., which are extruded and molded. The difference between the second hopper and the conventional one is that the conventional second hopper uses a small hopper because the blending rate of the filler and the like is extremely small relative to the blended amount of the pellets. Since the second hopper is charged with a large amount of spherical glass powder, the size of the second hopper should be equal to or larger than that of the first hopper of the pellet, and the spherical glass powder is preheated above the hopper. The difference is that a heating device (not shown) is provided. If the said heating apparatus can be heated in the range of 150 to 350 degreeC and can be controlled to a fixed temperature, the heating apparatus normally used can be used.

  The temperature of the filler, pigment, etc. to be charged into the conventional second hopper is used at room temperature, but is the spherical glass powder of the prior invention the same as the melting temperature of the thermoplastic resin before being charged into the second hopper? , Preheat to a temperature close to that, and then add. The preheating temperature is most preferably the same as the melting temperature, and (the melting temperature ± 10% temperature) is preferable. When the preheating temperature is lower than (the melting temperature−10% temperature), a large amount of glass powder takes heat from the molten thermoplastic resin, so that the fluidity may decrease, and the preheating temperature ( If the temperature is higher than the melting temperature + 10%, the viscosity resistance of the thermoplastic resin is too low and it may be in a liquid state and cannot be pelletized. Therefore, the preheating temperature of the glass powder is (melting temperature ± 10%). (Temperature) range is appropriate.

  First, according to the determined thermoplastic resin and glass blending ratio, the weight of the supplied pellets is weighed and put into the first hopper, and the pellets sent by kneading and conveying by the screw are in a molten state by the heater, That is, at the position where the second hopper is disposed, the spherical glass powder weighed to be supplied is preheated to a temperature equal to or close to the melting temperature of the thermoplastic resin and is put into the second hopper. The spherical glass powder charged into the molten thermoplastic resin is extruded while being kneaded to form a glass-containing molding composition, and then cut to obtain pellets.

  The temperature of the heater is determined according to the melting point of the thermoplastic resin used. For example, HD-PE is 230 ° C., PP is 220 ° C., PET is 250 ° C. Then, the number of rotations of the screw of the extruder was 200 times / minute while the compound was kneaded and extruded from a nozzle die having a diameter of 3 mm, which was made into a rod shape, cooled with water and cut into a length of 4 mm to obtain a pellet. It was.

(Spherical glass powder)
Examples of the glassy material of the spherical glass powder of the prior application invention include alkali glass, soluble glass, and alkali-free glass, in which one or more of SiO ₂ , B ₂ O ₃ , and P ₂ O ₃ are used as a net-forming product. . And in order to make the shape spherical, the distribution of the average particle diameter can be sharpened by using a method of pulverizing glass fibers. When the spherical glass powder has a high alkali content, the thermoplastic resin is likely to be embrittled. Therefore, a soluble glass having a low alkali content is preferable, and an alkali-free glass having no alkali content is more preferable.

  As the spherical glass powder, glass fiber having a diameter of 20 μm is used as a material. Since the diameter of the glass fiber is constant, a pulverized product having a diameter of 20 μm and a length of 10 to 30 μm is obtained by pulverizing the glass fiber so that the length of the glass fiber does not vary from the diameter of 20 μm. The pulverized product is sprayed into a 2500 to 3000 ° C. flame by an oxygen burner provided inside the furnace to be spheroidized, and the γ-glycidyloxypropylmethyldibenzene is formed into a sprayed sphere from a water injection device provided at the bottom of the furnace. Water containing 0.1% by weight of ethoxysilane was sprayed, silanized in a sprayed state, and collected with a bag filter. The collected glass powder is a spherical glass powder having a spherical average particle diameter of 10 to 40 μm. Thus, the spherical glass powder with an average particle diameter of 10-40 micrometers is obtained by using the said glass fiber whose diameter is 20 micrometers as a material. Hereinafter, the method of performing the silanization treatment performed in the spray state is referred to as “spray method”.

The spherical glass powder is obtained by silanizing the spherical glass powder by the spraying method. In other words, the spherical glass powder is characterized in that its surface is entirely covered with a silane compound.
Examples of the silane compound include those represented by the following formula.
R _4-n -Si- (OR ') _n
(In the formula, R represents an organic group, R ′ represents a methyl group, an ethyl group or a propyl group, and n represents an integer selected from 1 to 3).

  Examples of the silane compound include vinyltriethoxysilane, vinyltrimethoxysilane, γ-methacryloyloxypropyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, γ-glycidyloxypropyltrimethoxysilane, γ Silane coupling agents having an epoxy group such as glycidyloxypropylmethyldiethoxysilane, silane coupling agents having a mercapto group such as γ-mercaptopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, N-β (amino Examples include silane coupling agents having an amino group such as ethyl) γ-aminopropyltrimethoxysilane, N-β- (N-vinylbenzylaminoethyl) -γ-aminopropyltrimethoxysilane.

  Conventionally used glass powders are composed of various shapes such as polygons, rectangles, etc., and the average particle size is in a wide distribution range of 10 to 100 μm, whereas The glass powder of the claimed invention has a spherical shape, and its width is very small when the average particle diameter is in the range of 10 to 40 μm.

FIG. 2 is a graph showing the frequency of distribution of the average particle diameter of the spherical glass powder obtained by the above-described method for producing the spherical glass powder. The horizontal axis of this graph represents the particle size (μm) of the spherical glass powder, and the vertical axis represents the distribution frequency (%). The spherical E glass powder shows the highest distribution frequency when the particle size is 25 μm, and is distributed in a range of 10 to 40 μm on the normal distribution curve centering on the particle size of 25 μm. Is high.
FIG. 3 is a 1000 × electron micrograph of the spherical glass powder. From this photograph, it can be observed that the spherical glass powders are spherical in shape and have various particle sizes.
From the graph showing the frequency of the distribution of the average particle size of the spherical E glass powder in FIG. 2 and the photograph in FIG. 3, the spherical glass powder in the thermoplastic resin has a perfect circular spherical shape, and has various sizes. Although the thing of a diameter exists, it is shown that the average particle diameter is 10-40 micrometers.

  By the way, when the glass powder is put into the molten thermoplastic resin and kneaded, if the particle size is less than 10 μm, the proportion of fine particles increases, and the glass powder increases the amount of heat from the resin as the specific surface area increases. Because of this, the melt viscosity rises due to a sudden drop in the resin temperature, and the resin temperature during kneading rises extremely due to shearing heat generation, making it difficult to adjust the determined blending ratio of both materials. Become. In addition, by adding glass powder to the thermoplastic resin, in general, improvement of the dimensional stability, mechanical strength (impact strength, bending strength, etc.), warpage, transmission barrier properties, etc. of the molded body can be achieved. When the particle size is less than 10 μm, the bending strength is particularly lowered, which is not preferable.

  When the particle size is larger than 40 μm, the proportion of large particles increases, and the increase in melt viscosity during kneading is small, but when cutting the glass-containing composition into pellets of a certain size, the wear of the cutting blade becomes severe. Therefore, it becomes difficult to continuously produce a large amount of the glass-containing composition, resulting in production problems. Moreover, since the impact strength will fall especially when the particle size becomes larger than 40 micrometers, it is unpreferable. Therefore, the average particle size is preferably in the range of 10 to 40 μm.

(Thermoplastic resin)
As the thermoplastic resin, PE, PP, PET, PS, ABS, PVC, polycarbonate (hereinafter referred to as “PC”), polylactic acid (hereinafter referred to as “PLA”) or nylon (hereinafter referred to as “Ny”). ). In addition, any thermoplastic resin such as methacrylic resin, polyacetal, PBT, or PTT can be used.
By blending and kneading up to 70% by weight of spherical glass powder in a thermoplastic resin in a molten state, it is extruded into a 3mm diameter rod from a nozzle die provided at the discharge port of the extruder, cooled with water, and cutter Is cut into a length of about 4 mm to obtain a pellet-shaped glass-containing molding composition in which spherical glass powder is dispersed independently in the thermoplastic resin, but the diameter and length are limited to this. is not.

FIG. 4A is an electron micrograph of the glass-containing molding composition (pellet) produced by the above-described method for producing a glass-containing molding composition. This electron micrograph was taken by magnifying a cut part obtained by blending 50% by weight of spherical E glass powder into PP and cutting the pellet vertically from the side surface at a magnification of 50 times.
FIG. 4B is an electron micrograph taken with the cut portion magnified 100 times.
FIG. 4C is an electron micrograph taken by enlarging the side surface of the pellet 100 times.
From the photograph of the cut portion of the pellet in FIG. 4B, it is observed that the pellet is blended in the individual dispersed state in the PP without aggregation of individual spherical glass powders.
From this, the spherical glass powder is entirely coated with a silane compound by a spraying method, so that the pellets formed by kneading and extruding in an extruder are aggregated in the resin. It turned out that it was mix | blended in the state disperse | distributed independently without.

Then, a circle is drawn from the midpoint of the photograph in FIG. 4A to a position closer to the upper and lower ends, the circle is equally divided into 16, and the number of spherical glass powders blended in each of the 16 sections is visually counted. The counted results are shown in Table 1.
In addition, when spherical glass powder was present on the 16 dividing line, the number of spherical glass powders was calculated as 1/2.

From the measurement results in Table 1, the number of spherical glass powders in each section is in the range of 140 ± 1, indicating that the spherical glass powder is uniformly dispersed in the pellets.
From the above, in the glass-containing molding composition of the present invention, the glass powder has a spherical shape, an average particle size of 10 to 40 μm, and its surface is entirely covered with a silane compound, It was found that the glass blending ratio of the spherical glass powder charged in the thermoplastic resin was contained independently and uniformly dispersed.

Although a method for producing a glass-containing molding composition has been described in detail, if the method is to be described briefly and clearly, the production method is such that the silane compound is first entirely coated under high temperature heated spray conditions. In addition, the spherical glass powder was obtained, and the weight-measured thermoplastic resin was put into an extruder and melted, and the glass blending ratio 40 weighed and preheated into a region where the thermoplastic resin was in a molten state. A glass-containing molding composition is formed by putting ~ 70% by weight of the spherical glass powder into an extruder and kneading and extruding the charged spherical glass powder into a molten thermoplastic resin. it can.
In the above manufacturing method, an example of the best embodiment in which the spherical glass powder charged into the extruder is preheated to a temperature that is the same as or close to the melting temperature is shown, but the present invention is not limited to this example. The glass-containing molding composition of the present invention is also a glass-containing molding composition that is molded by a production method that controls the melting temperature (heating, cooling), screw speed, etc. used in conventional pellet molding. Is included.

Next, the sheet-like base material and glass-containing protective layer of the glass-containing thermal transfer sheet produced by the extrusion molding method using the glass-containing molding composition will be described below.
(Sheet substrate)
The sheet-like substrate for releasably adhering the glass-containing thermal transfer sheet used in the present invention uses a film containing spherical glass powder having a glass blending ratio of 40 to 70% by weight in a thermoplastic resin, but is conventionally used. It is also possible to use a sheet of paper or cellophane, PET, PA, PI or the like coated with a silicone-based adhesive such as polysiloxane, an acrylic pressure-sensitive adhesive, or a wax-based adhesive. it can.

(Glass-containing protective layer)
The glass-containing protective layer is formed by forming spherical glass powder 40 to 70% by weight and a functional filler into a thermoplastic resin and uniformly mixing pellets while maintaining a certain fluidity, and then extruding the pellets. A glass-containing protective layer is formed by (T-die or inflation).
Those effects cannot be obtained with a glass composition of 40% by weight or less. If the glass content is 70% by weight or more, the glass-containing protective layer is difficult to be formed and cannot be put into practical use.
Sheet-like base materials that use a glass-containing protective layer as a support have been used in many thermal transfer sheets, and are necessary for automatic work that performs in-mold transfer at the same time as molding inside a mold by in-mold molding. It is. As the sheet-like base material, for example, if a spherical glass powder containing PET is used, the thermal conductivity of the spherical glass powder is good, so that the efficiency of thermal bonding is improved.

Examples of the thermoplastic resin used for the glass-containing protective layer of the present invention include PE, Ny, PP, and PET. The thickness of the glass-containing protective layer is preferably 50 to 200 μm, more preferably 100 μm or less.
If you need flexibility, use LDPE. LLDPE fits. Printing or metal vapor deposition on the glass-containing protective layer to form a thermal transfer sheet is effective due to the see-through effect of the spherical glass powder.
In order to increase the hardness of the transfer surface to 2H or higher, it is preferable to add 50% by weight or more of spherical glass. The average particle size is preferably 2 to 40 μm, more preferably 10 to 20 μm. When the particle size is 2 μm or less, it is difficult to obtain hardness, and when the particle size is 40 μm or more, it is impossible to produce a glass-containing protective layer.
The thermal conductivity is improved by 34% or more when the spherical glass powder is mixed by 50% by weight or more, and the productivity is improved by shortening the thermal transfer time.

(Adhesive layer)
A hot melt adhesive is used for the adhesive layer. There are nylon-based, polyester-based, modified olefin-based, EVA-based, and rubber-based hot melt adhesives, and the softening temperature is arbitrarily selected from 90 ° C to 150 ° C. The adhesive layer is formed by melt-coating the glass-containing protective layer or by applying a liquid with a solvent. With the adhesive layer, the glass-containing protective layer can be transferred and adhered to plastic, metal, wood, paper, and ceramics by heat and pressure.
(Functional filler)
The functional filler of the present invention preferably has a particle size smaller than that of the spherical glass powder. 5A and 5B show electron micrographs of the surface of the glass-containing protective layer according to Example 3 of the present invention.

The unevenness of the surface seen in FIGS. 5A and 5B shows that when the molten resin is solidified during the production of the glass-containing protective layer, the resin between the spherical glass on the surface contracts due to the shrinkage force due to solidification, and the spherical glass protrudes. The surface becomes uneven. The surface of the spherical glass is coated with a resin containing a functional filler, and the functional filler projects to the surface together with the spherical glass, and the functional effect of the functional filler is obtained. When glass is not blended, due to the shrinkage force of solidification, the functional filler moves to the internal fluidity, and the functional filler moves under the resin surface film formed on the surface, so functionality Is difficult to obtain.
Antibacterial agents include silver zeolite, silver glass, and silver zirconium phosphate. Flame retardants include antimony trioxide, magnesium hydroxide, and aluminum hydroxide. Carbon fine powder and metal fine powder can be used for the antistatic agent, electric resistance agent, and conductive agent. Examples of the electromagnetic shielding agent include carbon fine powder, metal-coated carbon fine powder, nickel fine powder, and conductive fibrous fine particles.
The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples.

Example 1
The antibacterial thermal transfer sheet will be described below.
(1) Creation of glass-containing protective layer containing glass and silver antibacterial agent;
LDPE LJ802 (trade name: Nippon Polyethylene Co., Ltd.), silane-treated spherical glass powder (average particle size 20 μm) 40% by weight, and silver zeolite antibacterial agent AJ10N (average particle size 2-5 μm) (product) Name: Sinanen Zeomic Co., Ltd.) was blended with 0.1, 0.2, 0.4 wt% (with respect to LDPE wt%) and pelletized with an extruder. The pellets were extruded by an extruder (inflation) at a cylinder temperature of 180 ° C., a head temperature of 160 ° C., and a screw rotation speed of 120 rpm to produce a glass-containing protective layer having a thickness of 90 μm with an inflation rate of 10 times.
(2) The glass-containing protective layer containing the glass and the silver antibacterial agent is laminated on 20 μm of a PET sheet-like substrate containing 60% by weight of a spherical glass powder having an average particle diameter of 2 μm and coated with a silicone-based release adhesive. And adhered to each other in a peelable manner.
(3) The laminated glass-adhered surface of the glass-containing protective layer is subjected to an aluminum vapor deposition treatment, and HM223 (trade name; product of Cemedine Co., Ltd.) is applied thereon as an EVA hot melt, and the antibacterial thermal transfer sheet of Example 1 is applied. It was created.

The comparative example formed the protective layer which mix | blended the silver antibacterial agent which does not mix | blend spherical glass powder, and produced the thermal transfer sheet in the procedure similar to the above.
The produced thermal transfer sheet was inserted into a mold at the time of injection molding of a cosmetic compact container using ABS resin, and continuously thermally transferred onto the surface of the compact container by an in-mold method.
Table 1 shows the measured surface roughness, antibacterial properties, and thermal conductivity of the transfer surface of the container.

The surface roughness was measured based on JIS B 0610-1982, the maximum height measured by a three-dimensional roughness measuring device MODEL 3FK.
The antibacterial property was tested based on JIS Z2801. Escherichia coli (NBRC 3301). Staphylococcus aureus (NBRC 12732) was inoculated at 2.5 × 10 ⁵ cells / ml, cultured at 35 ° C. for 24 hours, washed out, and the number of viable bacteria was measured.
The pencil hardness is a measured value based on JIS K 5401.
The thermal conductivity was measured by a thermal conductivity measuring device (GH-D manufactured by Alpac Riko Co., Ltd.) based on ASTM E 1530.

  The surface roughness of Example 1 is 21.6 μm at the maximum height, the average roughness is 16.5 to 18.4 μm, and the roughness tends to increase with the stretch rate of inflation. As for the antibacterial property, the antibacterial property of Example 1 containing 0.1% silver zeolite (vs. PE%) is the antibacterial property corresponding to 0.4% (vs. PE%) of Comparative Example 1, which is clearly superior. There is sex. Although the thermal conductivity of PE is 0.303 W / m · K, it is 0.408 W / m · K by blending 50% by weight of spherical glass powder, which is an improvement of 34.6%.

FIG. 5A is an electron micrograph of the surface structure obtained by photographing the LDPE 50% by weight film of Example 1 from the vertical direction at a magnification of 100 times. FIG. 5B is an electron micrograph obtained by enlarging the surface structure of the film taken from a direction of 45 ° with a magnification of 100 times.
The photograph in FIG. 5A shows that the surface of the film is covered with a large number of spherical portions.
The photograph in FIG. 5B shows that the spherical portion is a large number of spherical convex portions protruding upward from the surface of the film, and that the region other than the spherical convex portion is composed of a flat portion made of a thermoplastic resin. Yes.

  From the photographs of FIGS. 5A and 5B, the film contains spherical glass powder at a glass blending ratio of 50% by weight, and the surface thereof is a flat portion made of the thermoplastic resin, and the thermoplastic resin is coated. It consists of a spherical convex part formed with many spherical glass powders formed, and the surface roughness is formed by this flat part and the spherical convex part.

(Example 2)
The flame retardant thermal transfer sheet will be described below.
(1) Glass-containing protective layer containing glass and flame retardant;
MH4 (trade name; Nippon Polypro Co., Ltd.) as PP, 50% by weight of silane-treated spherical glass powder (average particle size 20 μm), and antimony trioxide (Nippon Seiko Co., Ltd. product) as a flame retardant, 0.3,0.6,1.0% (vs. PP weight) was blended into pellets by an extruder, and the pellets were fed by an extruder (T die) at a cylinder temperature of 220 ° C., a head temperature of 240 ° C., and a screw rotation speed of 150 rpm. A glass-containing protective layer having a measured thickness of 70 μm was prepared by extrusion.

(2) The glass-containing protective layer was laminated and peeled and adhered using a paper coated with a silicone release adhesive as a sheet-like substrate.
(3) A wall cloth pattern is printed on the surface of the laminated glass-containing protective layer, and HM223 (product name: Cemedine Co., Ltd. product) is applied thereon as an EVA hot melt to provide an adhesive layer and flame retardant A thermal transfer sheet was prepared.

As a comparative example, a protective layer containing antimony trioxide not containing spherical glass powder was molded, and a thermal transfer sheet was prepared in the same procedure as described above.
The produced thermal transfer sheet was thermally transferred to a beer chloride sheet for building materials (thickness: 300 μm).
Table 2 shows the measured surface roughness, flame retardancy, and thermal conductivity of the transfer product.
The measurement conditions are the same as described in Example 1. In the flame retardancy test, a vertical combustion test based on US UL94 was conducted. In the evaluation, flame retardancy decreases in the order of V-0>V-1>V-2> HB, and V-0 is the highest.

The surface roughness of Example 2 is 16.5 μm at the maximum height, and the average roughness has a protrusion of 8.5 to 8.7 μm. Although flame retardance is HB at 0.3 wt% of the flame retardant of Comparative Example 2-1, Example 2-1 is improved to a level at which it is difficult to minimize fire spread at V-1. Due to the blending of glass and flame retardant, flame retardancy is obtained at low concentrations where no effect is conventionally obtained, and there is a clear difference. The thermal conductivity is 0.347 in Example 2 compared to 0.204 in Comparative Example 2, which is a 70% improvement.

(Example 3)
The antistatic thermal transfer sheet will be described below.
(1) a glass-containing protective layer containing glass and an antistatic agent;
IFG8L (trade name: Kanebo Co., Ltd.) as PET, 60% by weight of silane-treated spherical glass powder (average particle size: 15 μm), and carbon black (Mitsubishi Chemical Co., Ltd.) as an antistatic agent 0, 2.0% (vs PPET weight) was blended and pelletized by an extruder. The pellets were extruded by an extruder (inflation) at a cylinder temperature of 240 ° C., a head temperature of 250 ° C., and a screw rotation speed of 120 rpm to prepare a glass-containing protective layer having a measured thickness of 70 μm at a stretching ratio of 7 times.
(2) The glass-containing protective layer was laminated and peeled and adhered using a glass-containing protective layer having a PET thickness of 25 μm coated with a silicone-based release adhesive as a sheet-like substrate.
(3) A marble-like print is applied to the surface of the laminated glass-containing protective layer, and HM223 (product name: Cemedine Co., Ltd. product) is applied as an EVA hot melt on the surface to provide an adhesive layer to prevent static charge. A thermal transfer sheet was prepared.

As a comparative example, a protective layer containing carbon black containing no spherical glass powder was molded, and a thermal transfer sheet was prepared in the same procedure as described above.
The produced thermal transfer sheet was thermally transferred to a rubber sheet laid on the floor.
The surface roughness, antistatic property, and thermal conductivity of the transfer product were measured and shown in Table 3.
The measurement conditions are the same as those described in Example 1, but for antistatic properties, the electrical resistivity of the surface was measured by applying a high resistivity meter MCP-HT260 (manufactured by Dia Instruments) with an applied voltage of 500V. The surface resistivity was measured based on JISK6911 with a charging time of 1 minute.

The surface roughness of Example 3 is significantly rougher than that of the comparative example, which is due to the protrusion of the spherical glass powder. From the surface resistivity, the antistatic property is not obtained in Comparative Example 3, but the excellent antistatic property is obtained in the Examples with the same concentration, and the difference from the conventional one is obvious. The thermal conductivity is improved by 115%.

BRIEF DESCRIPTION OF THE DRAWINGS It is a longitudinal cross-sectional view of the single screw extruder which is an example of the extruder used for the manufacturing method which shape | molds the glass-containing shaping | molding composition of prior invention, and manufactures the composition. It is a logarithm graph which shows the frequency of distribution of the average particle diameter of spherical E glass powder. It is an electron micrograph of 1000 times of spherical E glass powder. It is the electron micrograph which expanded and image | photographed the cutting part which cut | disconnected the glass containing molding composition (pellet) manufactured with the manufacturing method of the glass containing molding composition perpendicularly | vertically from the side surface. It is the electron microscope photograph which expanded and image | photographed the cutting part which cut | disconnected the said pellet perpendicularly | vertically from the side surface 100 times. It is the electron micrograph which expanded and image | photographed the side surface of the said pellet 100 times. It is the electron micrograph which image | photographed the surface structure which image | photographed LDPE50 weight% film from the perpendicular direction by enlarging 100 times. It is the electron micrograph which image | photographed the surface structure which image | photographed LDPE50 weight% film from the direction of 45 degrees of inclination, expanding 100 times.

Claims (7)

A glass-containing thermal transfer sheet in which a release layer, a protective layer and an adhesive layer are provided in a laminated form on a sheet-like substrate,
The protective layer contains spherical glass powder having a glass blending ratio of 40 to 70% by weight and a functional filler in a thermoplastic resin, and the surface of the protective layer is a flat portion made of the thermoplastic resin, and its thermoplasticity. A glass-containing thermal transfer sheet comprising a spherical convex portion formed of a large number of spherical glass powders coated with a resin, wherein a part of the functional filler protrudes from the flat portion and the spherical convex portion.   2. The glass-containing thermal transfer sheet according to claim 1, wherein the sheet-like substrate is a film containing spherical glass powder having a glass blending ratio of 40 to 70% by weight in a thermoplastic resin.   2. The glass-containing thermal transfer sheet according to claim 1, wherein one of the sheet-like base materials is selected from paper or a film of cellophane, PET, PA, or PI.   The said functional filler is 1 type, or 2 or more types selected from the antibacterial agent, the flame retardant, the antistatic agent, the electromagnetic wave shielding agent, and the electrically conductive agent, The claim any one of Claims 1 thru | or 3 characterized by the above-mentioned. The glass-containing thermal transfer sheet according to item.   The glass-containing thermal transfer sheet according to any one of claims 1 to 4, wherein a particle size of the functional filler is smaller than the spherical glass powder.   The glass-containing thermal transfer sheet according to any one of claims 1 to 4, wherein the glass-containing protective layer is printed or vapor-deposited.   The glass-containing thermal transfer sheet according to any one of claims 1 to 3, wherein the spherical glass powder has an average particle size of 2 to 40 µm.